Cyclohexenone derivatives and their use for controlling undesirable plant growth

ABSTRACT

Cyclohexenone derivatives of the formula ##STR1## where R 1  is hydrogen, methoxycarbonyl, ethoxycarbonyl, methyl or cyano, R 2  is alkyl, R 3  is alkyl, alkenyl, haloalkenyl, or propargyl, R 4  is hydrogen or alkyl, R 5  is hydrogen, alkyl, acyl, formyl, cycloalkylcarbonyl, methoxyalkylcarbonyl, unsubstituted or substituted benzoyl, alkoxycarbonyl, benzyloxycarbonyl, phenoxycarbonyl, alkylthiocarbonyl, N,N-dialkylcarbamyl, N-alkylcarbamyl, N-cycloalkylcarbamyl, N-alkoxy-N-alkylcarbamyl, unsubstituted or substituted N-phenylcarbamyl, alkylsulfonyl, alkenylsulfonyl, haloalkylsulfonyl, N-alkylsulfamyl, N,N-dialkylsulfamyl, N-acyl-N-alkylsulfamyl, N-alkyl-N-methoxycarbonylsulfamyl, dialkoxyphosphoryl, dialkoxythiophosphoryl, 2-haloalkanoyl, acyloxyacetyl or alkoxyoxalyl, and R 6  is alkyl, halogen, hydroxyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro or amino, and salts of these compounds, and the use of these compounds for controlling unwanted plant growth.

The present invention relates to cyclohexenone derivatives, herbicides which contain these compounds as active ingredients, and a method of controlling undesirable plant growth.

It has been disclosed that cyclohexenone derivatives can be used for controlling undesirable grasses in broad-leaved crops (DE-A No. 2 439 104). Furthermore, DE-A No. 3 248 554 discloses that cyclohexen-1-one derivatives which carry a para-substituted phenyl ring in the 5-position control gramineous weeds in corn and wheat.

We have found that cyclohexenone derivatives of the formula I ##STR2## where R¹ is hydrogen, methoxycarbonyl, ethoxycarbonyl, methyl or cyano, R² is alkyl of 1 to 4 carbon atoms, R³ is alkyl of 1 to 4 carbon atoms, alkenyl of 3 or 4 carbon atoms, haloalkenyl of 3 or 4 carbon atoms which possesses 1 to 3 halogen substituents, or propargyl, R⁴ is hydrogen or alkyl of 1 to 4 carbon atoms, R⁵ is hydrogen, alkyl, aliphatic acyl of 2 to 8 carbon atoms, formyl, cycloalkylcarbonyl of 4 to 7 carbon atoms, methoxyalkylcarbonyl, or benzoyl which is unsubstituted or substituted by nitro, halogen, alkyl or alkoxy, or is alkoxycarbonyl, benzyloxycarbonyl, phenoxycarbonyl, alkylthiocarbonyl, N,N-dialkylcarbamyl, N-alkylcarbamyl, N-cycloalkylcarbamyl where cycloalkyl is of 5 to 8 carbon atoms, N-alkoxy-N-alkylcarbamyl, N-phenylcarbamyl which is unsubstituted or substituted by nitro, halogen, alkyl, alkoxy or haloalkyl, or is alkylsulfonyl, alkenylsulfonyl, haloalkylsulfonyl, N-alkylsulfamyl, N,N-dialkylsulfamyl, N-acyl-N-alkylsulfamyl where acyl is of 2 to 5 carbon atoms, N-alkyl-N-methoxycarbonylsulfamyl, dialkoxyphosphoryl, dialkoxythiophosphoryl, 2-haloalkanoyl, acyloxyacetyl or alkoxyoxalyl, and R⁶ is alkyl, halogen, hydroxyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro or amino, and salts of these compounds possess a good herbicidal action, preferably against species from the grass family (gramineae). 3 or 4 carbon atoms which may contain not more than 3 halogen substituents, preferably chloroalkenyl, eg. methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, allyl, 1-chloroprop-1-en-3-yl, 2-chloroprop-1-en-3-yl, 1,3-dichloroprop-1-en-3-yl or 1,1,2-trichloroprop-1-en-3-yl, R⁴ is hydrogen or alkyl of 1 to 4 carbon atoms, ie. methyl, ethyl, propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, preferably hydrogen, R⁵ is hydrogen, alkyl, aliphatic acyl of 2 to 8 carbon atoms, formyl, cycloalkylcarbonyl of 4 to 7 carbon atoms, methoxyalkylcarbonyl of 3 to 7 carbon atoms, benzoyl which is unsubstituted or substituted by nitro, halogen, alkyl or alkoxy, alkoxycarbonyl, benzyloxycarbonyl, phenoxycarbonyl, alkylthiocarbonyl, N,N-dialkylcarbamyl, N-alkylcarbamyl, N-cycloalkylcarbamyl where cycloalkyl is of 5 to 8 carbon atoms, N-alkoxy-N-alkylcarbamyl, or N-phenylcarbamyl which is unsubstituted or substituted by nitro, halogen, alkyl, alkoxy or haloalkyl, or is alkylsulfonyl, alkenylsulfonyl of 2 to 4 carbon atoms, haloalkylsulfonyl, haloalkenylsulfonyl of 2 to 4 carbon atoms, N-alkylsulfamyl, N,N-dialkylsulfamyl, N-acyl-N-alkylsulfamyl where acyl is of 2 to 5 carbon atoms, N-alkyl-N-methoxycarbonylsulfamyl, dialkoxyphosphoryl, dialkoxythiophosphoryl, 2-haloalkanoyl of 2 to 5 carbon atoms, acyloxyacetyl, where acyl is of 2 to 4 carbon atoms, or alkoxyoxalyl, preferably hydrogen, aliphatic acyl of 2 to 8 carbon atoms, or benzoyl which is unsubstituted or substituted by nitro, halogen, alkyl or alkoxy, particularly preferably hydrogen, acetyl or benzoyl, and R⁶ is in the ortho-, meta or para-position and is halogen, hydroxyl or alkyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkylsulfinyl, or alkylsulfonyl, each of which is of not more than 4 carbon atoms, or nitro or amino, preferably halogen in particular fluorine or chlorine.

The alkyl groups R⁵ and R⁶, and the alkyl and alkoxy groups in the radicals stated for R⁵ and R⁶, may be straight-chain or branched and, unless stated otherwise, are each of 1 to 4 carbon atoms, ie. suitable alkyl and alkoxy groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec.-butoxy and tert.-butoxy.

R⁵ is, for example, hydrogen, methyl, ethyl, acetyl, propionyl, butyryl, valeryl, formyl, cyclopropylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, methoxyacetyl, 2-methoxypropionyl, 3-methoxypropionyl, benzoyl, 3-nitrobenzoyl, 2-chlorobenzoyl, 4-methylbenzoyl, 4-methoxybenzoyl, methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, phenoxycarbonyl, methylthiocarbonyl, ethylthiocarbonyl, isopropylthiocarbonyl, N,N-dimethylcarbamyl, N-methylcarbamyl, N-cyclohexylcarbamyl, N-methoxy-N-methylcarbamyl, N-(4-nitrophenyl)-carbamyl, N-(2-chlorophenyl)carbamyl, N-(3-methylphenyl)-carbamyl, N-(3-methoxyphenyl)carbamyl, N-methylsulfamyl, N,N-dimethylsulfamyl, N,N-diethylsulfamyl, N-acetyl-N-methylsulfamyl, N-butyryl-N-ethylsulfamyl, N-methoxycarbonyl-N-methylsulfamyl, N-isopropyl-N-methoxycarbonylsulfamyl, methylsulfonyl, chloromethylsulfonyl, trifluoromethylsulfonyl, prop-2-en-ylsulfonyl, 2,3,3-trichloroprop-2-en-ylsulfonyl, diethoxyphosphoryl, diethoxythiophosphoryl, chloroacetyl, 2-bromopropionyl, acetoxyacetyl, ethoxyoxalyl.

R⁶ is, for example, methyl, ethyl, n-propyl, n-butyl, isopropyl, sec.-butyl, isobutyl, tert.-butyl, fluorine, chlorine, bromine, iodine, hydroxyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, secbutoxy, tert.-butoxy, allyloxy, prop-2-ynyloxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, nitro or amino.

Suitable salts of the compounds of the formula I are agriculturally useful salts, for example the alkali metal salts, in particular the potassium and sodium salts, alkaline earth metal salts, in particular calcium, magnesium and barium salts, manganese salts, copper salts, zinc salts and iron salts and ammonium and phosphonium salts, eg. alkylammonium, dialkylammonium, trialkylammonium or tetraalkylammonium salts, benzyltrialkylammonium salts, triphenylphosphonium salts, trialkylsulfonium salts and trialkylsulfoxonium salts.

The herbicidal cyclohexenone derivatives of the formula I can be obtained by reacting a tricarbonyl compound of the formula II ##STR3## with an ammonium compound R³ O--NH₃ Y, where R³ has the above meanings and Y is an anion.

The reaction is advantageously carried out in the heterogeneous phase in an inert diluent at from 0° to 80° C. or from 0° C. to the boiling point of the reaction mixture, in the presence of a base. Examples of suitable bases are carbonates, bicarbonates, acetates, alcoholates, hydroxides and oxides of alkali metals and alkaline earth metals, in particular of sodium, potassium, magnesium and calcium. Organic bases, such as pyridine or tertiary amines, can also be used.

The reaction proceeds particularly well at a pH of from 2 to 9, in particular from 4.5 to 5.5. The pH is advantageously established by adding an acetate, for example an alkali metal acetate, in particular sodium or potassium acetate or a mixture of the two salts. Alkali metal acetates are added, for example, in amounts of from 0.5 to 2 moles per mole of the ammonium compound of the formula R³ O--NH₃ Y.

Examples of suitable solvents are dimethyl sulfoxide, alcohols, such as methanol, ethanol or isopropanol, benzene, hydrocarbons or chlorohydrocarbons, such as chloroform, dichloroethane, hexane or cyclohexane, esters, such as ethyl acetate, and ethers, such as dioxane or tetrahydrofuran.

The reaction is complete after a few hours, and the product can be isolated by evaporating down the mixture, adding water and extracting with a non-polar solvent, such as methylene chloride, and distilling off the solvent under reduced pressure.

The compounds of the formula I may furthermore be obtained by reacting a tricarbonyl compound of the formula II with a hydroxylamine of the formula R³ O--NH₂, where R³ has the above meanings, in an inert diluent at from 0° C. to the boiling point of the reaction mixture, in particular from 15° to 70° C. If necessary, the hydroxylamine can be used in the form of an aqueous solution.

Examples of suitable solvents for this reaction are alcohols, such as methanol, ethanol, isopropanol or cyclohexanol, hydrocarbons or chlorohydrocarbons, such as hexane, cyclohexane, methylene chloride, toluene or dichloroethane, esters, such as ethyl acetate, nitriles, such as acetonitrile, and cyclic ethers, such as tetrahydrofuran.

The alkali metal salts of the compounds of the formula I can be obtained by treating these compounds with sodium hydroxide or potassium hydroxide in aqueous solution or in an organic solvent, such as methanol, ethanol or acetone. Sodium alcoholates and potassium alcoholates may also serve as bases.

The other metal salts, eg. the manganese, copper, zinc, iron, calcium, magnesium and barium salts, can be prepared from the sodium salts by reaction with the corresponding metal chlorides in aqueous solution. Ammonium, phosphonium, sulfonium and sulfoxonium salts can be prepared by reacting a compound of the formula I with an ammonium, phosphonium, sulfonium or sulfoxonium hydroxide, if necessary in aqueous solution.

The novel tricarbonyl compounds of the formula II can be prepared from cyclohexane-1,3-diones of the formula ##STR4## where R¹, R⁴, R⁵ and R⁶ have the above meanings, by methods known from the literature (Tetrahedron Letters, 29, (1975), 2491).

It is also possible to obtain the novel compounds of the formula II via the enol-ester intermediates, which may be obtained as isomer mixtures in the acylation of compounds of the formula VII and undergo rearrangement in the presence of imidazole or pyridine derivatives (JP-A No.-63 052/1979).

As can be seen from the above statements, the novel tricarbonyl compounds of the formula II are useful intermediates for the preparation of the herbicidal compounds of the formula I.

The compounds of the formula VII are in turn obtained by methods known from the literature, as is evident from the scheme below: ##STR5##

The cyclohexenone derivatives of the formula Ia ##STR6## and the tricarbonyl compounds of the formula II ##STR7## where R¹ and R⁴ are each hydrogen, R² is alkyl of 1 to 4 carbon atoms, R³ is alkyl of 1 to 4 carbon atoms, alkenyl of 3 or 4 carbon atoms, haloalkenyl of 3 or 4 carbon atoms which possesses 1 to 3 halogen substituents, or propargyl, R⁵ is aliphatic acyl of 2 to 8 carbon atoms, formyl, cycloalkylcarbonyl of 4 to 7 carbon atoms, methoxyalkylcarbonyl, or benzoyl which is unsubstituted or substituted by nitro, halogen, alkyl or alkoxy, or is alkoxycarbonyl, benzyloxycarbonyl, phenoxycarbonyl, alkylthiocarbonyl, N,N-dialkylcarbamyl, N-alkoxy-N-alkylcarbamyl, alkylsulfonyl, alkenylsulfonyl, haloalkylsulfonyl, N-alkylsulfamyl, N,N-dialkylsulfamyl, N-acyl-N-alkylsulfamyl where acyl is of 2 to 5 carbon atoms, N-alkyl-N-methoxycarbonylsulfamyl, dialkoxyphosphoryl, dialkoxythiophosphoryl, 2-haloalkanoyl, acyloxyacetyl or alkoxyoxalyl, and R⁶ is alkyl, halogen, hydroxyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro or amino, can be obtained by reacting a compound of the formula Ia or II, where R⁵ is hydrogen, with an electrophilic reagent of the formula R 5_(Y) (III), where R⁵ has the above meanings and Y is a leaving group, such as chlorine, bromine or carboxylate.

The reaction is, if necessary, carried out in an inert organic solvent, examples of suitable solvents being hydrocarbons, such as naphtha, gasoline, toluene, pentane, cyclohexane, halohydrocarbons, such as methylene chloride, chloroform, dichloroethane, chlorobenzene or o-, m- or p-dichlorobenzene, nitrohydrocarbons, such as nitrobenzene or nitromethane, nitriles, such as acetonitrile, butyronitrile or benzonitrile, ethers, such as diethyl ether, tetrahydrofuran or dioxane, esters, such as ethyl acetate or methyl propionate, ketones, such as acetone or methyl ethyl ketone, and amides, such as N,N-dimethylformamide or formamide, and mixtures of these solvents. The amount of solvent is from 100 to 5,000% by weight, based on aniline derivative employed.

Advantageously, the reaction is carried out in the presence of a conventional acid acceptor, suitable compounds being alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, alkaline earth metal hydroxides, alkaline earth metal carbonates, alkaline earth metal bicarbonates, alkaline earth metal oxides and amines, eg. sodium bicarbonate, potassium carbonate, triethylamine, tributylamine, pyridine, N,N-dimethylaniline, N,N-dimethyl-N-cyclohexylamine or quinoline. The amount of acid acceptor is from 1 to 4 moles per mole of aniline derivative employed.

The reaction temperature is from -20° to +150° C., preferably from 20° to 80° C. The electrophilic reagents R⁵ Y and the compounds of the formula Ia and II which are used as starting compounds are preferably employed in equimolar amounts.

Examples of compounds of the formula R⁵ Y are acyl halides, carboxylic anhydrides, chloroformates, alkylthiocarbonyl chlorides, N,N-dialkylcarbamyl chlorides, N-alkoxy-N-alkylcarbamyl chlorides, N-alkylsulfamyl chlorides and N-acyl-N-alkylsulfamyl chlorides, such as acyl halides of the formula

    R.sup.8 --CO--Hal,

where R⁸ is alkyl of 1 to 7 carbon atoms, cycloalkyl of 3 to 5 carbon atoms, methoxyalkyl of 2 to 4 carbon atoms or phenol which is unsubstituted or substituted by nitro, halogen, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 3 carbon atoms, formic acetic anhydride of the formula ##STR8## chloroformates of the formula

    R.sup.9 O--CO--Cl,

where R⁹ is alkyl of 1 to 4 carbon atoms, benzyl or phenyl, alkylthiocarbonyl chlorides of the formula

    R.sup.10 S--CO--Cl,

N,N-dialkylaminocarbamyl chlorides of the formula where R¹⁰ is alkyl of 1 to 4 carbon atoms, ##STR9## where R¹¹ and R¹² are each alkyl of 1 to 4 carbon atoms, N-alkoxy-N-alkylcarbamyl chlorides of the formula ##STR10## where R¹³ is alkyl of 1 to 4 carbon atoms and R¹⁴ is alkoxy of 1 to 4 carbon atoms, sulfonyl chlorides of the formula

    R.sup.15 --SO.sub.2 Cl,

where R¹⁵ is alkyl of 1 to 4 carbon atoms, alkenylsulfonyl of 3 or 4 carbon atoms, or haloalkylsulfonyl of not more than 3 halogen atoms, sulfamyl chlorides of the formula ##STR11## where R¹⁶ is alkyl of 1 to 4 carbon atoms and R¹⁷ is hydrogen, alkyl of 1 to 4 carbon atoms, acyl of 2 to 5 carbon atoms or methoxycarbonyl, dialkoxyphosphoryl or dialkoxythiophosphoryl chlorides of the formula ##STR12## where X is O or S, and R¹⁸ and R¹⁹ are each alkyl of 1 to 4 carbon atoms, 2-haloalkanoyl chlorides of the formula ##STR13## where R²⁰ and R²¹ are each H or alkyl of 1 to 4 carbon atoms and Hal is fluorine, chlorine, bromine or iodine, acyloxyacetyl chlorides of the formula ##STR14## where R²² is alkyl of 1 to 4 carbon atoms, and alkoxyoxalyl chlorides of the formula ##STR15## where R²³ is alkyl of 1 to 4 carbon atoms.

Furthermore, the cyclohexenone derivatives of the formula Ic ##STR16## and the tricarbonyl compounds of the formula II ##STR17## where R¹ and R⁴ are each hydrogen, R² is alkyl of 1 to 4 carbon atoms, R⁵ is N-alkylcarbamyl, N-cycloalkylcarbamyl, where cycloalkyl is of 5 to 8 carbon atoms, or N-phenylcarbamyl which is unsubstituted or substituted by nitro, halogen, alkyl or alkoxy, and R⁶ is alkyl, halogen, hydroxyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro or amino, are obtained by reacting the corresponding amino derivative with an isocyanate of the formula

    R.sup.7 --NCO                                              (IV),

where R⁷ is a radical which leads to appropriate radicals R⁵ in formulae I and II when the reaction is complete.

The reaction is carried out in the presence or absence of a catalyst conventionally used for isocyanate reactions, for example a tertiary amine, such as triethylamine or 1,4-diazabicyclo[2.2.2]octane, nitrogen-containing heterocycles, such as pyridine or 1,2-dimethylimidazole, or organo-tin compounds, such as dibutyl-tin diacetate or dimethyl-tin dichloride, and in the presence or absence of a solvent which is inert under the reaction conditions, for example a hydrocarbon, such as naphtha, gasoline, toluene, pentane or cyclohexane, a halohydrocarbon, such as methyl chloride, chloroform, dichloroethane, chlorobenzene or o-, m- or p-dichlorobenzene, a nitrohydrocarbon, such as nitrobenzene or nitromethane, a nitrile, such as acetonitrile, butyronitrile or benzonitrile, in ether, such as diethyl ether, tetrahydrofuran or dioxane, an ester, such as ethyl acetate or methyl propionate, a ketone, such as acetone or methyl ethyl ketone, or an amide, such as N,N-dimethylformamide or formamide (Houben-Weyl, Methoden der organischen Chemie, vol. VIII, page 132, Georg Thieme-Verlag, Stuttgart, 4th edition, 1952).

The amount of catalyst is from 0.1 to 5 mol %, based on the aniline derivative employed. The amount of solvent varies from 100 to 10,000% by weight. The reaction temperature can vary from -20° to +150° C., preferably from 0° to 100° C.

The catalytic hydrogenation of nitro compounds of the formula V gives the corresponding amino compounds of the formula Ib: ##STR18## This reaction is carried out in the presence or absence of an inert solvent, eg. tetrahydrofuran, dioxane, a C₁ -C₄ -alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, N,N-dimethylformamide, pyridine, ethyl acetate, acetone, water or a mixture of these, under from 1 to 5 bar, preferably under atmospheric pressure, with the addition of a conventional hydrogenation catalyst, such as palladium, platinum or nickel, at from 0° to 80° C., preferably at room temperature.

The derivatives of the formula VI which are required for the preparation of the compounds V can be obtained by various methods: ##STR19##

The position at which the nitro group is introduced into the dicarbonyl or tricarbonyl intermediate depends critically on R⁶, in accordance with the rules of electrophilic aromatic substitution, for example: ##STR20##

The Examples which follow illustrate the preparation of the cyclohexenone derivatives of the formula I.

EXAMPLE 1

5.3 g of 2-butyryl-5-(3-nitro-4-methoxyphenyl)cyclohexane-1,3-dione in 300 ml of tetrahydrofuran were hydrogenated in the presence of 3 g of Pd/carbon (10%) under atmospheric pressure at 25° C. After 0.9 l of hydrogen had been absorbed, the mixture was dried over sodium sulfate and filtered, 1.3 g of sodium bicarbonate were added and the mixture was reacted with 1.2 g of acetyl chloride. After the mixture had been stirred for 16 hours, it was filtered and evaporated down. The remaining oil was brought to crystallization with diethyl ether, and the crystals were filtered off under suction. 3 g (55% yield) of 5-(3-acetylamino-4-methoxyphenyl)-2-butyryl-3-hydroxycyclohex-2-en-1-one of melting point 102°-106° C. were obtained.

EXAMPLE 2

3 g of 5-(3-acetylamino-4-methoxyphenyl)-2-butyryl-3-hydroxycyclohex-2-en-1-one were stirred together with 0.95 g of O-allylhydroxylamine hydrochloride and 0.8 g of sodium bicarbonate in 40 ml of methanol for 16 hours. The mixture was evaporated down, mixed with methylene chloride, washed thoroughly with water, dried and evaporated down again. The residue which remained was stirred with diisopropyl ether and the product was filtered off under suction. 2.0 g (57% yield) of 5-(3-acetylamino-4-methoxyphenyl)-2-(1-allyloxyiminobutyl)-3-hydroxycyclohex-2-en-1-one of melting point 136°-137° C. were obtained (compound No. 11).

EXAMPLE 3

1.3 g of methanesulfonyl chloride were added to 4 g of 2-(1-ethoxyiminobutyl)-3-hydroxy-5-(3-amino-4-methoxyphenyl)-cyclohex-2-en-1-one in 50 ml of pyridine at 25° C., and the reaction solution was stirred for 16 hours, poured onto ice and brought to pH 1 with hydrochloric acid. The mixture was extracted with methylene chloride, and the organic phase was dried and evaporated down to give 3.6 g (74% yield) of 2-(1-ethoxyiminobutyl)-3-hydroxy-5-(4-methoxy-3-methoxysulfonamidophenyl)-cyclohex-2-en-1-one of melting point 108°-116° C. (decomposition) (compound No. 64).

EXAMPLE 4

4 g of 5-(3-amino-4-methoxyphenyl)-2-(1-ethoxyiminobutyl)-3-hydroxycyclohex-2-en-1-one in 50 ml of pyridine were stirred with 2.2 g of diethoxythiophosphoryl chloride for 16 hours at 25° C., and the reaction solution was poured onto ice and brought to pH 1 with hydrochloric acid. The mixture was extracted with methylene chloride, and the solution was filtered over silica gel and evaporated down to give 4 g (69% yield) of an oil consisting of 5-(3-diethoxythiophosphorylamido-4-methoxyphenyl)-2-(1-ethoximinobutyl)-3-hydroxycyclohex-2-en-1-one (compound No. 76).

EXAMPLE 5

4 g of 5-(3-amino-4-methoxyphenyl)-2-(1-ethoxyiminobutyl)-3-hydroxycyclohex-2-en-1-one in 50 ml of pyridine were stirred with 1.5 g of methylaminosulfonyl chloride for 16 hours at 25° C., and the reaction solution was poured onto ice and brought to pH 1 with hydrochloric acid. The mixture was extracted with methylene chloride and the organic phase was dried and evaporated down to give 2.2 g (43% yield) of 2-(1-ethoxyiminobutyl)-3-hydroxy-5-(4-methoxy-3-N-methyl-sulfamylamido)-cyclohex-2-en-1-one of melting point 56°-58° C. (compound No. 75).

EXAMPLE 6

31 g of 2-acetyl-3-hydroxy-5-(2-methoxyphenyl)cyclohex-2-en-1-one were dissolved in 140 ml of glacial acetic acid, 140 ml of concentrated sulfuric acid were added to the cooled solution at 25° C., 7.7 g of 98% strength nitric acid were rapidly added dropwise, the mixture was stirred for 30 minutes and then poured into an ice/methylene chloride mixture, and the organic phase was separated off, washed with water and dried over sodium sulfate. The dark oil obtained when the solution was evaporated down was dissolved in methylene chloride and then filtered over silica gel, and the solution was evaporated down to give 27.5 g (76% yield) of yellowish crystals consisting of 20% of 2-acetyl-3-hydroxy-5-(2-methoxy-3-nitrophenyl)-cyclohex-2-en-1-one (A) and 80% of 2-acetyl-3-hydroxy-5-(2-methoxy-5-nitrophenyl)-cyclohex-2-en-1-one (B) and having a mixed melting point of 145°-151° C. ##STR21##

15 g of the above product mixture consisting of A and B in a ratio of 1:4 were stirred together with 4.2 g of sodium bicarbonate and 4.6 g of O-ethylhydroxylammonium chloride in methanol for 16 hours, the mixture was evaporated down, the residue was taken up in methylene chloride, the solution was extracted by shaking with water, dried and evaporated down. The residue was triturated in diisopropyl ether and the product was filtered off under suction. 15.5 g (91% yield) of the corresponding O-ethyloxime ethers C and D were obtained, once again in the form of a 1:4 mixture (mixed melting point 132°-142° C.). ##STR22##

10.3 g of the 1:4 product mixture of C and D in 500 ml of tetrahydrofuran were hydrogenated in the presence of 3 g of palladium on carbon (10%) under atmospheric pressure at 25° C. After 3 l of hydrogen had been absorbed, the mixture was dried over sodium sulfate, filtered and evaporated down. 9.5 g of an oily 1:4 mixture of the corresponding anilines E and F were obtained, the yield being quantitative. ##STR23##

9 g of this aniline mixture were dissolved in 50 ml of tetrahydrofuran, 2.4 g of sodium bicarbonate were added and the stirred mixture was reacted with 2.2 g of acetyl chloride. Stirring was continued for 16 hours, after which the mixture was filtered, the filtrate was evaporated down and the oil which remained was chromatographed over silica gel using ethyl acetate. 0.9 g (9% yield) of the pure 5-(3-acetamido-2-methoxyphenyl)-2-(1-ethoximinoethyl)-3-hydroxycyclohex-2-en-1-one isomer, ##STR24## and 3.6 g (35% yield) of the pure 5-(5-acetamido-2-methoxyphenyl)-2-(1-ethoxyiminoethyl)-3-hydroxycyclohex-2-en-1-one isomer, ##STR25## were obtained.

EXAMPLE 7

60 g of 5-(2-fluorophenyl)-cyclohexane-1,3-dione were dissolved in 500 ml of concentrated sulfuric acid at -20° C. and nitrated with 18.3 g of 98% strength nitric acid at -20° C. in the course of 60 minutes. The reaction mixture was stirred into 5 l of ice water, and the precipitated crystals were filtered off under suction and dried. 60.5 g (83% yield) of 5-(2-fluoro-5-nitrophenyl)-cyclohexane-1,3-dione of melting point 171°-173° C. were obtained.

54 g of the above product were dissolved in 500 ml of methylene chloride, 18.7 g of pyridine were added and O-acylation was carried out at room temperature in the course of 1 hour using 25.2 g of butyryl chloride. The mixture was stirred for 16 hours, after which it was extracted by shaking with ice water, with 5% strength sodium bicarbonate solution and again with ice water, dried over sodium sulfate and evaporated down. The oil which remained was taken up in about 300 ml of ethyl acetate and left to stand together with 3 g of 4-dimethylaminopyridine for 5 days. The organic phase was extracted twice by shaking with 5% strength hydrochloric acid, dried and evaporated down. The residue which remained was recrystallized from isopropanol to give 33 g (48% yield) of 2-butyryl-5-(2-fluoro-5-nitrophenyl)-3-hydroxycyclohex-2-en-1-one of melting point 132° C.

25 g of the above product, 7.4 g of sodium bicarbonate and 8.6 g of O-ethylhydroxylammonium chloride in 100 ml of methanol were stirred for 16 hours, the mixture was evaporated down, the residue was taken up in methylene chloride, and the solution was washed with water, dried and evaporated down again. 24 g (84% yield) of 2-(1-ethoximinobutyl)-5-(2-fluoro-5-nitrophenyl)-3-hydroxycyclohex-2-en-1-one were obtained as a viscous oil.

23 g of this oil in 500 ml of tetrahydrofuran were hydrogenated in the presence of 5 g of palladium on carbon (10%) under atmospheric pressure at 25° C. After 4.5 l of hydrogen had been absorbed, the mixture was dried, filtered and evaporated down. 19.6 g (93% yield) of 5-(5-amino-2-fluorophenyl)-2-(1-ethoximinobutyl)-3-hydroxycyclohex-2-en-1-one were obtained as a viscous oil.

5.5 g of this product in 50 ml of tetrahydrofuran were left to stand together with 1 g of methyl isocyanate and 1 drop of dibutyl-tin diacetate for 4 days at room temperature. The mixture was evaporated down and the residue was stirred thoroughly with ether and dried. 4.4 g (69% yield) of 2-(1-ethoximinobutyl)-5-[2-fluoro-5-(3-methylureido)-phenyl]-3-hydroxycyclohex-2-en-1-one of melting point 120°-122° C. were obtained (compound No. 116).

The following cyclohexenone derivatives of the formula I were obtained in a similar manner:

    __________________________________________________________________________     Compound                                                                       No.   R.sup.5           R.sup.1                                                                              R.sup.2                                                                            R.sup.3      R.sup.4                                                                           M.p. [°C.]            __________________________________________________________________________      ##STR26##                                                                      1    H                 H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  76-78                         2    H                 H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                                3    H                 H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                                4    H                 H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                                5    methyl            H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             CH.sub.3                         6    methyl            H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          CH.sub.3                         7    acetyl            H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  139-141                       8    acetyl            COOCH.sub.3                                                                          C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  54-61                         9    acetyl            H     CH.sub.3                                                                           C.sub.2 H.sub.5                                                                             H  130-133                       10   acetyl            H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  124-126                       11   acetyl            H     C.sub.3 H.sub.7                                                                    CH.sub.2 CHCH.sub.2                                                                         H  136-137                       12   butyryl           H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                                13   butyryl           H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                                14   butyryl           H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                                15   butyryl           H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                                16   formyl            H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  117-118                       17   formyl            H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                                18   formyl            H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                                19   formyl            H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                                20   formyl            H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCHCl                                                                              H                                21   cyclopropylcarbonyl                                                                              H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  131-135                       22   cyclopropylcarbonyl                                                                              H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                                23   cyclopropylcarbonyl                                                                              H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                                24   cyclopropylcarbonyl                                                                              H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                                25   methoxyacetyl     H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  138-140                       26   methoxyacetyl     H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                                27   methoxyacetyl     H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                                28   methoxyacetyl     H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  127-130                       29   3-methoxypropionyl                                                                               H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  93-97                         30   3-methoxypropionyl                                                                               H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                                31   3-methoxypropionyl                                                                               H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                                32   3-methoxypropionyl                                                                               H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                                33   benzoyl           H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  110-112                       34   benzoyl           H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                                35   benzoyl           H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                                36   benzoyl           COOCH.sub.3                                                                          C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                                 37  3-nitrobenzoyl    H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                                38   3-methoxybenzoyl  H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                                39   4-chlorobenzoyl   H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                                40   methoxycarbonyl   H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  110-113                       41   methoxycarbonyl   H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                                42   methoxycarbonyl   H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                                43   methoxycarbonyl   H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  125-127                       44   methylthiocarbonyl                                                                               H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  106-108                       45   methylthiocarbonyl                                                                               H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                                46   methylthiocarbonyl                                                                               H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                                47   methylthiocarbonyl                                                                               H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  118-120                       48   chloroacetyl      H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  125-130                       49   2-bromopropionyl  H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  139-142                       50   ethoxyoxalyl      H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  118-120                        51  acetoxyacetyl     H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  117-122                       52   N,Ndimethylcarbamoyl                                                                             H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                                53   N,Ndimethylcarbamoyl                                                                             H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                                54   N,Ndimethylcarbamoyl                                                                             H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                                55   N,Ndimethylcarbamoyl                                                                             H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                                56   Nmethylcarbamoyl  H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  105-107                       57   Nmethylcarbamoyl  H     n-C.sub.3 H.sub.7                                                                  CH.sub.2 CHCH.sub.2                                                                         H                                58   Nmethylcarbamoyl  H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                                59   Nmethylcarbamoyl  COOCH.sub.3                                                                          C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  80-82                         60   NmethoxyNmethylcarbamoyl                                                                         H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  96-99                         61   NmethoxyNmethylcarbamoyl                                                                         COOCH.sub.3                                                                          C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  85-107                        62   NmethoxyNmethylcarbamoyl                                                                         H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                                63   NmethoxyNmethylcarbamoyl                                                                         H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  91-93                         64   methylsulfonyl    H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  108-116                                                                        (decomp.)                     65   methylsulfonyl    H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                                66   methylsulfonyl    H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                                67   methylsulfonyl    H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  168-170                       68   trifluoromethylsulfonyl                                                                          H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                                69   trifluoromethylsulfonyl                                                                          H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                                70   trifluoromethylsulfonyl                                                                          H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                                71   trifluoromethylsulfonyl                                                                          H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                                72   chloromethylsulfonyl                                                                             H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                                73   chloromethylsulfonyl                                                                             H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                                74   N-isobutylsulfamoyl                                                                              H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                                75   N-methylsulfamoyl H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  56-58                         76   diethoxythiophosphoryl                                                                           H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  (NMR data)                    77   diethoxyphosphoryl                                                                               H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  (NMR data)                   136   H                 COOCH.sub.3                                                                          C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  (NMR data)                   137   H                 H     CH.sub.3                                                                           C.sub.2 H.sub.5                                                                             H  118-121                      138   methoxyacetyl     H     CH.sub.3                                                                           C.sub.2 H.sub.5                                                                             H  120-124                      139   benzoyl           H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  120-121                      140   benzoyl           H     CH.sub.3                                                                           C.sub.2 H.sub.5                                                                             H  134-139                      141   acetoxyacetyl     H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  103-105                      142   Nmethylcarbamoyl  H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  143-146                       ##STR27##                                                                      78   H                 H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  oil                           79   H                 H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                                80   Nmethylcarbamoyl  H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub. 5                                                                            CH.sub.3                         81   acetyl            H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                                82   acetyl            H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                               143   acetyl            H     n-C.sub.3 H.sub.7                                                                  n-C.sub.3 H.sub.7                                                                           H  69-72                        144   benzoyl           H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  112-114                      145   methoxyacetyl     H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  95-99                         ##STR28##                                                                      83   H                 H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                                84   H                 H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                                85   H                 H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                                86   H                 H     CH.sub.3                                                                           C.sub.2 H.sub.5                                                                             H  oil                           87   H                 H     CH.sub.3                                                                           CH.sub.2CHCH.sub.2                                                                          H                                88   methyl            H     n-C.sub.3 H.sub. 7                                                                 C.sub.2 H.sub.5                                                                             CH.sub.3                         89   methyl            H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          CH.sub.3                         90   methyl            H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          CH.sub.3                         91   acetyl            H     CH.sub.3                                                                           C.sub.2 H.sub.5                                                                             H  124-126                      146   acetyl            H     C.sub.2 H.sub.3                                                                    C.sub.2 H.sub.5                                                                             H                               147   acetyl            H     C.sub.2 H.sub.5                                                                    CH.sub.2 CH.sub.2 Cl                                                                        H                               148   acetyl            H     C.sub.2 H.sub.5                                                                    (E)-CH.sub.2CHCHCH.sub.3                                                                    H                               149   acetyl            H     C.sub.2 H.sub.5                                                                    (E)-CH.sub.2CHCHCH.sub.3                                                                    H                               150   acetyl            H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                               151   acetyl            H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  96-98                        152   acetyl            H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CH.sub.2 Cl                                                                         H                               153   acetyl            H     n-C.sub.3 H.sub.7                                                                  CH.sub.2 CH.sub.2 F                                                                         H                               154   acetyl            H     n-C.sub.3 H.sub.7                                                                  (E)-CH.sub.2CHCHCH.sub.3                                                                    H                               155   acetyl            H     n-C.sub.3 H.sub.7                                                                  (E)-CH.sub.2CHCHCl                                                                          H                               156   acetyl            H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                               157   propionyl         H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                               158   propionyl         H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                               159   propionyl         H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                               160   propionyl         H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               161   butyryl           H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                               162   butyryl           H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                               163   butyryl           H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                               164   butyryl           H     n-C.sub.3 H.sub.7                                                                  C.sub.5 H.sub.5                                                                             H                               165   chloroacetyl      H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               166   chloroacetyl      H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                               167   chloroacetyl      H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                               168   chloroacetyl      H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                               169   methoxyacetyl     H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                               170   methoxyacetyl     H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                               171   methoxyacetyl     H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                               172   methoxyacetyl     H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               173   benzoyl           H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               174   benzoyl           H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                               175   benzoyl           H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                               176   benzoyl           H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                                ##STR29##                                                                      92   H                 H     CH.sub.3                                                                           C.sub.2 H.sub.5                                                                             H  oil                           93   H                 H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                                94   H                 H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                                95   acetyl            H     CH.sub.3                                                                           C.sub.2 H.sub.5                                                                             H  152-153                       96   acetyl            H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  133-135                       97   acetyl            H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  138-140                       98   methoxycarbonyl   H     CH.sub.3                                                                           C.sub.2 H.sub.5                                                                             H  129-133                       99   methoxycarbonyl   H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  106-108                      100   methoxycarbonyl   H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                               101   methylthiocarbonyl                                                                               H     CH.sub.3                                                                           C.sub.2 H.sub.5                                                                             H  134-136                      102   methylthiocarbonyl                                                                               H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               177   3-methoxypropionyl                                                                               H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  (NMR data)                   178   3-methoxypropionyl                                                                               H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                               179   benzoyl           H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  179-180                      180   benzoyl           H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  134-136                      103   Nmethylcarbamoyl  H     CH.sub.3                                                                           C.sub.2 H.sub.5                                                                             H  167-169                      104   Nmethylcarbamoyl  H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  156-158                      105   Nmethylcarbamoyl  H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  180-181                      106   NmethoxyNmethylcarbamoyl                                                                         H     CH.sub.3                                                                           C.sub.2 H.sub.5                                                                             H  118-120                      107   NmethoxyNmethylcarbamoyl                                                                         H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  84-87                         ##STR30##                                                                     108   H                 H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  (NMR data)                   109   acetyl            H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  119                          110   acetyl            H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                               111   Nmethylcarbamoyl  H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  152-153                      112   Nmethylcarbamoyl  H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                               181   Nmethylcarbamoyl  H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                               182   Nmethylcarbamoyl  H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  139-142                      183   NmethoxyNmethylcarbamoyl                                                                         H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  120-123                      184   NmethoxyNmethylcarbamoyl                                                                         H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               185   methylthiocarbonyl                                                                               H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  130-132                      186   methylthiocarbonyl                                                                               H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               187   methoxycarbonyl   H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  105-109                      188   methoxycarbonyl   H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                               189   methoxycarbonyl   H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                               190   methoxycarbonyl   H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  131-134                      191   chloroacetyl      H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  128-129                      192   chloroacetyl      H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                               193   chloroacetyl      H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                               194   chloroacetyl      H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               195   methoxyacetyl     H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  (NMR data)                   196   methoxyacetyl     H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                               197   methoxyacetyl     H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                               198   methoxyacetyl     H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  158-160                      199   acetoxyacetyl     H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  123-125                      200   acetoxyacetyl     H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                               201   acetoxyacetyl     H     C.sub.2 H.sub.5                                                                    CH.sub.2 CH.sub.2 Cl                                                                        H                               202   acetoxyacetyl     H     C.sub.2 H.sub.5                                                                    (E)-CH.sub.2CHCHCH.sub.                                                                     H                               203   acetoxyacetyl     H     C.sub.2 H.sub.5                                                                    (E)-CH.sub.2CHCHCl                           204   acetoxyacetyl     H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               205   acetoxyacetyl     H     n-C.sub.3 H.sub.7                                                                  CH.sub.2 CHCH.sub.2                                                                         H                               206   acetoxyacetyl     H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CH.sub.2 Cl                                                                         H                               207   acetoxyacetyl     H     n-C.sub.3 H.sub.7                                                                  (E)-CH.sub.2 CHCHCH.sub.3                                                                   H                               208   acetoxyacetyl     H     n-C.sub.3 H.sub.7                                                                  (E)-CH.sub.2CHCHCl                                                                          H                               209   propioxyacetyl    H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               210   propioxyacetyl    H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                               211   benzoyloxyacetyl  H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                               212   benzoyloxyacetyl  H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               213   benzoyl           H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  145-148                      214   benzoyl           H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  123-126                      215   methylsulfonyl    H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  126-130                      216   methylaminosulfonyl                                                                              H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  145-148                      217   acetyl            H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  153-156                       ##STR31##                                                                     113   H                 H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  (NMR data)                   114   acetyl            H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  120-122                      115   benzoyl           H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  116-117                      116   Nmethylcarbamoyl  H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  120-122                       ##STR32##                                                                     117   acetyl            H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  120-122                      118   methylsulfonyl    H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               119   chloromethylsulfonyl                                                                             H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               120   trifluoromethylsulfonyl                                                                          H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               218   H                 H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  (NMR data)                   219   chloroacetyl      H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  111-115                      220   chloroacetyl      H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                               221   chloroacetyl      H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                               222   chloroacetyl      H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                               223   acetyl            H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                               224   acetyl            H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H  109-111                      225   acetyl            H     C.sub.2 H.sub.5                                                                    CH.sub.2 CH.sub.2 Cl                                                                        H                               226   acetyl            H     n-C.sub.3 H.sub.7                                                                  (E)-CH.sub.2CHCHCH.sub.3                                                                    H  121-123                      227   acetyl            H     C.sub.2 H.sub.5                                                                    (E)-CH.sub.2CHCHCl                                                                          H                               228   methoxyacetyl     H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  94-96                        229   methoxyacetyl     H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                               230   methoxyacetyl     H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                               231   methoxyacetyl     H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub. 2                                                                         H                               232   acetyl            H     n-C.sub.3 H.sub.7                                                                  (E)-CH.sub.2CHCHCl                                                                          H  128-130                      233   benzoyl           H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                               234   benzoyl           H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                               235   benzoyl           H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                               236   benzoyl           H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  125-128                      237   3-methoxypropionyl                                                                               H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  112-114                      238   3-methoxypropionyl                                                                               H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                               239   methoxycarbonyl   H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                               240   methoxycarbonyl   H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  (NMR data)                   241   methylthiocarbonyl                                                                               H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  94-97                        242   methylthiocarbonyl                                                                               H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                               243   Nmethylcarbamoyl  H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               244   Nmethylcarbamoyl  H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  117-121                      245   NmethoxyNmethylcarbamoyl                                                                         H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  83-86                        246   NmethoxyNmethylcarbamoyl                                                                         H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                               247   methylsulfonyl    H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                               248   methylsulfonyl    H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               249   methylaminosulfonyl                                                                              H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  (NMR data)                   250   methylaminosulfonyl                                                                              H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                               251   propionyl         H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               252   propionyl         H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                               253   butyryl           H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               254   butyryl           H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                               255   cyclohexylcarbonyl                                                                               H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               256   cyclohexylcarbonyl                                                                               H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                               257   N,Ndimethylcarbamoyl                                                                             H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               258   N,Ndimethylcarbamoyl                                                                             H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               259   ethoxycarbonyl    H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               260   ethoxycarbonyl    H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                               __________________________________________________________________________     Compound                                                                       no.   R.sup.6                                                                               R.sup. 5   R.sup.1                                                                              R.sup.2                                                                            R.sup.3      R.sup.4                                                                           M.p. [°C.]            __________________________________________________________________________      ##STR33##                                                                     121   chlorine                                                                              acetyl     H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  136-139                      122   hydroxy                                                                               acetyl     H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  125-126                      123   tert.-butoxy                                                                          acetyl     H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               124   allyloxy                                                                              acetyl     H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               125   propargyloxy                                                                          acetyl     H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               261   hydroxy                                                                               H          H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                               262   hydroxy                                                                               acetyl     H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  144-146                      263   hydroxy                                                                               chloroacetyl                                                                              H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  170-172                      264   hydroxy                                                                               benzoyl    H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  150-152                      265   hydroxy                                                                               benzoyl    H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  122-126                      266   hydroxy                                                                               Nmethylcarbamoyl                                                                          H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  108-110                      267   chlorine                                                                              H          H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  138 (decomp.)                268   chlorine                                                                              acetyl     H     n-C.sub.3 H.sub.7                                                                  (E)-CH.sub.2CHCHCl                                                                          H  78-80                        269   chlorine                                                                              benzoyl    H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  124-127                      270   chlorine                                                                              methoxyacetyl                                                                             H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  98-103                       271   chlorine                                                                              chloroacetyl                                                                              H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  96-101                       130   ethylthio                                                                             acetyl     H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               131   ethylthio                                                                             benzoyl    H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               132   ethylsulfynyl                                                                         acetyl     H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               133   ethylsulfynyl                                                                         benzoyl    H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               134   ethylsulfynyl                                                                         acetyl     H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               135   ethylsulfynyl                                                                         benzoyl    H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                                ##STR34##                                                                     126   nitro  acetyl     H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  118-120                      127   nitro  acetyl     H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                               128   amino  acetyl     H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               129   amino  acetyl     H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                               272   nitro  benzoyl    H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               273   nitro  benzoyl    H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               274   amino  benzoyl    H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               275   amino  benzoyl    H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                               276   chlorine                                                                              benzoyl    H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               277   chlorine                                                                              benzoyl    H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                               278   chlorine                                                                              acetyl     H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               279   chlorine                                                                              acetyl     H     n-C.sub.3 H.sub.7                                                                  CH.sub.2 CHCH.sub.2                                                                         H                               280   bromine                                                                               acetyl     H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               281   bromine                                                                               acetyl     H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                               282   bromine                                                                               benzoyl    H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               283   bromine                                                                               benzoyl    H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                               284   fluorine                                                                              benzoyl    H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H  151-153                      285   fluorine                                                                              benzoyl    H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                               286   fluorine                                                                              benzoyl    H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                           287   fluorine                                                                              benzoyl    H     C.sub.2 H.sub.5                                                                    (E)-CH.sub.2CHCHCl                                                                          H  156-157                      288   fluorine                                                                              benzoyl    H     C.sub.2 H.sub.5                                                                    (E)-CH.sub.2CHCHCH.sub.3                                                                    H                               289   fluorine                                                                              benzoyl    H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  163-165                      290   fluorine                                                                              benzoyl    H     n-C.sub.3 H.sub.7                                                                  CH.sub.2 CH.sub.2 Cl                                                                        H                               291   fluorine                                                                              benzoyl    H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H  121-123                      292   fluorine                                                                              benzoyl    H     n-C.sub.3 H.sub.7                                                                  (E)-CH.sub.2CHCHCl                                                                          H  108-112                      293   fluorine                                                                              benzoyl    H     n-C.sub.3 H.sub.7                                                                  (E)-CH.sub. 2CHCHCH.sub.3                                                                   H                               294   fluorine                                                                              o-toluyl   H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               295   fluorine                                                                              o-toluyl   H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                               296   fluorine                                                                              o-toluyl   H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                               297   fluorine                                                                              o-toluyl   H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                               298   fluorine                                                                              acetyl     H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                               299   fluorine                                                                              acetyl     H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                               300   fluorine                                                                              acetyl     H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               301   fluorine                                                                              acetyl     H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                               302   fluorine                                                                              H          H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  oil                           ##STR35##                                                                     303   fluorine                                                                              benzoyl    H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                               304   fluorine                                                                              benzoyl    H     C.sub.2 H.sub.5                                                                    CH.sub.2 CH.sub.2 Cl                                                                        H                               305   fluorine                                                                              benzoyl    H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                               306   fluorine                                                                              benzoyl    H     C.sub.2 H.sub.5                                                                    (E)-CH.sub.2CHCHCl                                                                          H                               307   fluorine                                                                              benzoyl    H     C.sub.2 H.sub.5                                                                    (E)-CH.sub.2CHCHCH.sub.3                                                                    H                               308   fluorine                                                                              benzoyl    H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H  (NMR data)                   309   fluorine                                                                              benzoyl    H     n-C.sub.3 H.sub.7                                                                  CH.sub.2 CH.sub.2 Cl                                                                        H                               310   fluorine                                                                              benzoyl    H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                               311   fluorine                                                                              benzoyl    H     n-C.sub.3 H.sub.7                                                                  (E)-CH.sub.2CHCHCl                                                                          H                               312   fluorine                                                                              benzoyl    H     n-C.sub.3 H.sub.7                                                                  (E)-CH.sub.2CHCHCH.sub.3                                                                    H                               313   chlorine                                                                              benzoyl    H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                             H                               314   chlorine                                                                              benzoyl    H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                          H                               315   chlorine                                                                              benzoyl    H     n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                             H                               316   chlorine                                                                              benzoyl    H     n-C.sub.3 H.sub.7                                                                  CH.sub.2CHCH.sub.2                                                                          H                               __________________________________________________________________________

The cyclohexenone derivatives of the formula I may be identified by characteristic ¹ H-NMR spectroscopic data (chemical shift in δ values (ppm) in CDCl₃, based on tetramethylsilane as internal standard; s=singlet, d=doublet, q=quartet, m=multiplet):

    ______________________________________                                         Compound no. Characteristic signals                                            ______________________________________                                          76          1.0 (t, 3H); 3.9 (s, 3H); 4.0-4.4 (m, 6H)                          77          1.0 (t, 3H); 3.85 (s, 3H); 4.0-4.3 (m, 6H)                         91          2.2 (s, 3H); 2.45 (s, 3H); 3.75 (s, 3H);                                       6.95 (d, 1H); 7.15 (t, 1H); 8.20 (d, 1H)                           95          2.2 (s, 3H); 2.4 (s, 3H); 3.8 (s, 3H);                                         6.8 (d, 1H); 7.45 (d, 1H)                                         108          0.95 (t, 3H); 4.1 (q, 2H); 6.55 (d, 1H);                                       6.75 (s, 1H); 7.10 (d, 1H)                                        113          1.3 (t, 3H); 6.4-6.6 (m), 6.85 (t)                                136          3.6 (s); 3.8 (s); 6.5-6.8 (m)                                     177          2.95 (t); 6.8 (d); 7.25 (m); 7.45 (m),                                         8.35 (s)                                                          195          2.15 (s); 3.4 (s); 8.1 (s); 6.9-7.1 (m);                                       7.85 (d)                                                          218          0.95 (t); 1.3 (t); 4.05-4.2 (q)                                   240          2.95 (t); 3.35 (m);, 3.8 (s); 4.15 (q)                            249          0.95 (t); 4.1 (q); 4.75 (q); 6.7 (s);                                          7.4 (d)                                                           308          2.97 (t); 4.12 (q); 7.86 (d).                                     ______________________________________                                    

The cyclohexenone derivatives of the formula I, and their salts, may be applied for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or other suspensions), dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used, but they must ensure as fine a distribution of the active ingredients according to the invention as possible.

For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.

Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, haptadecanols, and octadecanols, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.

Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.

The formulations contain from 0.1 to 95, and preferably 0.5 to 90, % by weight of active ingredient.

Examples of formulations are given below.

I. 90 parts by weight of compound no. 1 is mixed with 10 parts by weight of N-methyl-alpha-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

II. 20 parts by weight of compound no. 7 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

III. 20 parts by weight of compound no. 109 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

IV. 20 parts by weight of compound no. 111 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210° and 280° C., and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

V. 20 parts by weight of compound no. 7 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained containing 0.1% by weight of the active ingredient.

VI. 3 parts by weight of compound no. 33 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.

VII. 30 parts by weight of compound no. 56 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

VIII. 20 parts of compound no. 111 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.

IX. 10 parts of compound no. 289 is mixed with 90 parts by weight of a mixture of 93 parts by weight of xylene and 7 parts by weight of the adduct of 8 moles of ethylene oxide and 1 mole of nonyl phenol. A solution is obtained which contains 10 wt% of active ingredient.

The active ingredients, or agents containing them, may be applied pre- or postemergence. If certain crop plants tolerate the active ingredients less well on post-emergence treatment, application techniques may be used in which the herbicidal agents are sprayed from suitable equipment in such a manner that the leaves of sensitive crop plants are if possible not touched, and the agents reach the soil or the unwanted plants growing beneath the crop plants (post-directed, lay-by treatment).

The amount of active ingredient applied depends on the time of the year, the plants to be combatted and their growth stage, and varies from 0.025 to 3 kg/ha, but is preferably from 0.06 to 0.5 kg/ha.

The action of the cyclohexenone derivatives of the formula I on plant growth is demonstrated in greenhouse experiments.

The vessels employed were plastic flowerpots having a volume of 300 cm³, and which were filled with a sandy loam containing about 1.5% humus. The seeds of the test plants were sown shallow, and separately, according to species. For the preemergence treatment, the active ingredients were applied to the surface of the soil immediately after the seeds had been sown. The compounds were emulsified or suspended in water as vehicle, and sprayed through finely distributing nozzles. The application rate was 3.0 kg of active ingredient per hectare. After the agents had been applied, the vessels were lightly sprinkler-irrigated to induce germination and growth. Transparent plastic covers were then placed on the vessels until the plants had taken root. The cover ensured uniform germination of the plants, insofar as this was not impaired by the active ingredients.

For the postemergence treatment, the plants were first grown in the vessels to a height of from 3 to 15 cm, depending on growth form, before being treated. The soybean plants were grown in a peat-enriched substrate. For this treatment, either plants which had been sown directly in the pots and grown there were selected, or plants which had been grown from seedlings and were transplanted to the pots a few days before treatment. The application rates for postemergence treatment were 0.06 to 0.5 kg of active ingredient per hectare. No covers were placed on the vessels in this method.

The pots were set up in the greenhouse--species from warmer areas at from 20° to 35° C., and species from moderate climates at 10° to 25° C. The experiments were run for 2 to 4 weeks. During this period, the plants were tended and their reactions to the various treatments assessed. The scale used for assessment was 0 to 100, 0 denoting no damage or normal emergence, and 100 denoting nonemergence or complete destruction of at least the visible plant parts.

The plants used in the experiments were Alopecurus myosuroides, Avena fatua, Avena sativa, Echinochloa crus-galli, Glycine max., Lolium multiflorum, Oryza sativa, Setaria italica, Sinapis alba, and Sorghum halepense.

On preemergence application, for example compounds nos. 1, 7, 33 and 56 proved to be herbicidally effective on plants from the grasses family, whereas Sinapis alba, as a dicotyledonous representative, remained completely undamaged.

On postemergence application, for instance compounds nos. 56 and 114 at 0.5 kg/ha, and nos. 109 and 111 at 0.06 kg/ha had a strong herbicidal action on grasses selected by way of example, whereas soybeans, as dicotyledonous crop plants, were not damaged. Compound no. 7 is, for example, suitable for combatting Echinochloa crus-galli in rice.

Unwanted grasses can be controlled with small amounts of, for instance, compounds nos. 109 and 111; soybeans as dicotyledonous crop plants, remained undamaged.

Compounds nos. 60, 64 and 75 selected by way of example combatted unwanted grassy plants well, and were tolerated well by soybeans.

Compound no. 103, for instance, had a high level of action on plants from the Gramineae family and caused no damage to wheat.

Unwanted grassy plants can be combatted well with compounds nos. 117, 126 and 127 selected by way of example. Alfalfa as crop plant suffered no damage.

For example compound no. 289 is suitable for controlling important grassy weeds in rice. Only slight damage was caused to the crop plant.

In view of the spectrum of weeds which can be combatted, the tolerance of the active ingredients according to the invention by crop plants, the desired influence on the growth of crop plants, and in view of the numerous application methods possible, the cyclohexenone derivatives of the formula I may be used in a large number of crop plants.

The following may be mentioned by way of example:

    ______________________________________                                         Botanical name      Common name                                                ______________________________________                                         Allium cepa         onions                                                     Ananas comosus      pineapples                                                 Arachis hypogaea    peanuts (groundnuts)                                       Asparagus officinalis                                                                              asparagus                                                  Avena sativa        oats                                                       Beta vulgaris spp. altissima                                                                       sugarbeets                                                 Beta vulgaris spp. rapa                                                                            fodder beets                                               Beta vulgaris spp. esculenta                                                                       table beets, red beets                                     Brassica napus var. napus                                                                          rapeseed                                                   Brassica napus var. napobrassica                                                                   swedes                                                     Brassica napus var. rapa                                                                           turnips                                                    Brassica rapa var. silvestris                                                  Camellia sinensis   tea plants                                                 Carthamus tinctorius                                                                               safflower                                                  Carya illinoinensis pecan trees                                                Citrus limon        lemons                                                     Citrus maxima       grapefruits                                                Citrus reticulata   mandarins                                                  Citrus sinensis     orange trees                                               Coffea arabica (Coffea canephora,                                                                  coffee plants                                              Coffea liberica)                                                               Cucumis melo        melons                                                     Cucumis sativus     cucumbers                                                  Cynodon dactylon    Bermudagrass in turf                                                           and lawns                                                  Daucus carota       carrots                                                    Elais guineensis    oil palms                                                  Fragaria vesca      strawberries                                               Glycine max         soybeans                                                   Gossypium hirsutum  cotton                                                     (Gossypium arboreum                                                            Gossypium herbaceum                                                            Gossypium vitifolium)                                                          Helianthus annuus   sunflowers                                                 Helianthus tuberosus                                                                               Jerusalem artichoke                                        Hevea brasiliensis  rubber plants                                              Hardeum vulgare     barley                                                     Humulus lupulus     hops                                                       Ipomoea batatas     sweet potatoes                                             Juglans regia       walnut trees                                               Lactuca sativa      lettuce                                                    Lens culinaris      lentils                                                    Linum usitatissimum flax                                                       Lycopersicon lycopersicum                                                                          tomatoes                                                   Malus spp.          apple trees                                                Manihot esculenta   cassava                                                    Medicago sativa     alfalfa (lucerne)                                          Mentha piperita     peppermint                                                 Musa spp.           banana plants                                              Nicothiana tabacum  tobacco                                                    (N. rustica)                                                                   Olea europaea       olive trees                                                Oryza sativa        rice                                                       Panicum miliaceum                                                              Phaseolus lunatus   limabeans                                                  Phaseolus mungo     mungbeans                                                  Phaseolus vulgaris  snapbeans, green beans,                                                        dry beans                                                  Pennisetum glaucum                                                             Petroselinum crispum                                                                               parsley                                                    spp. tuberosum                                                                 Picea abies         Norway spruce                                              Abies alba          fir trees                                                  Pinus spp.          pine trees                                                 Pisum sativum       English peas                                               Prunus avium        cherry trees                                               Prunus domestica    plum trees                                                 Prunus dulcis       almond trees                                               Prunus persica      peach trees                                                Pyrus communis      pear trees                                                 Ribes sylvestre     redcurrants                                                Ribes uva-crispa    gooseberries                                               Ricinus communis    castor-oil plants                                          Saccharum officinarum                                                                              sugar cane                                                 Secale cereale      rye                                                        Sesamum indicum     sesame                                                     Solanum tuberosum   Irish potatoes                                             Sorghum bicolor (s. vulgare)                                                                       sorghum                                                    Sorghum dochna      sorgo                                                      Spinacia oleracea   spinach                                                    Theobroma cacao     cacao plants                                               Trifolium pratense  red clover                                                 Triticum aestivum   wheat                                                      Vaccinium corymbosum                                                                               blueberries                                                Vaccinium vitis-idaea                                                                              cranberries                                                Vicia faba          tick beans                                                 Vigna sinensis (V. unguiculata)                                                                    cow peas                                                   Vitis vinifera      grapes                                                     Zea mays            Indian corn, sweet                                                             corn, maize                                                ______________________________________                                    

To increase the spectrum of action and to achieve synergistic effects, the cyclohexenone derivatives of the formula I, and their salts, may be mixed and applied together with numerous representatives of other hericidal or growth-regulating active ingredient groups. Examples of suitable mixture components are diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, benzofuran derivatives, quinolinecarboxylic acid derivatives, etc.

It may also be useful to apply the compounds of the formula I, either alone or in combination with other herbicides, in admixture with other crop protection agents, e.g., agents for combatting pests or phytopathogenic fungi or bacteria. The compounds may also be mixed with solutions of mineral salts used to remedy nutritional or trace element deficiencies. Non-phytotoxic oils and oil concentrates may also be added. 

We claim:
 1. A cyclohexenone of the formula ##STR36## wherein R⁶ is a member selected from the group consisting of chlorine, bromine and fluorine and R² is a member selected from the group consisting of ethyl and n-propyl.
 2. The composition of claim 1 wherein R⁶ is fluorine and R² is member selected from the group consisting of ethyl and n-propyl.
 3. A cyclohexenone of the formula ##STR37## 